CN104162431A - Roll forming type egg shell type catalyst - Google Patents
Roll forming type egg shell type catalyst Download PDFInfo
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- CN104162431A CN104162431A CN201410451833.XA CN201410451833A CN104162431A CN 104162431 A CN104162431 A CN 104162431A CN 201410451833 A CN201410451833 A CN 201410451833A CN 104162431 A CN104162431 A CN 104162431A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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Abstract
The invention relates to a roll forming type egg shell type catalyst. The egg shell type catalyst can be used in the occasions of a methanolysis process with coupling heat absorption and a Fischer-Tropsch synthesis process with heat release, so that methyl alcohol is directly converted into diesel fraction; a shell layer of the egg shell type catalyst is made of an active component with a methanolysis function, and an inner core of the egg shell type catalyst is made of an active component with a Fischer-Tropsch synthesis function; and furthermore, in the roll forming process, a heat conduction additive is added into the egg shell type catalyst, so that the heat exchange effect in catalyst particles can be improved.
Description
Technical field
The invention provides a kind of egg-shell catalyst of the moulding of rolling, be specifically related to a kind of solid catalyst with nucleocapsid structure for Methanol diesel oil.
Background technology
In chemical reaction, can be with the generation of heat release or endothermic process.Solving the heat problem of transmission in course of reaction, is one of groundwork of chemical production technical.
Methanol Decomposition is that the reaction (CH3OH → CO+2H2) of synthesis gas is the reaction of a heat absorption.Consider from thermodynamics, high temperature is conducive to methyl alcohol to carry out to the direction that is decomposed into synthesis gas.
The process of a heat release by synthesis gas through the synthetic process of producing diesel component of Fischer-Tropsch, consider from improving the selective angle of diesel component, cryogenic high pressure is conducive to the synthetic diesel oil of producing of Fischer-Tropsch, so in actual production operating process, Fischer-Tropsch is synthetic to carry out between 200 DEG C to 250 DEG C, and takes reaction heat out of reactor by various heating picking process.
The synthesis gas that Methanol Decomposition is obtained is through the synthetic diesel oil that changes into of Fischer-Tropsch, this process route is in the relatively oversaturated situation in coal methyl alcohol processed market, a part of methanol conversion can be become to diesel fuel, form one parallel mutually with preparing gasoline by methanol technique, widen the new technology of the application surface of Coal Chemical Industry.This technique needs the catalyst synergy of two kinds of effects, namely carbinol resolving catalyst and fischer-tropsch synthetic catalyst, and bifunctional catalyst is a kind of approach that realizes this technique.The method of preparing bifunctional catalyst has multiple, has plenty of the component with different catalysis is evenly mixed to moulding, for example powder blend aftershaping or the preparation of total immersion stain.The catalyst of preparing by the way, the effect of influencing each other between wherein each kind of component has often changed the function of original active component existing with independent form, the function that is to say the catalyst forming after mixing is not the original stack of catalysis separately, but the change of matter has occurred.Obviously for Methanol Decomposition preparing synthetic gas again Fischer-Tropsch synthetic the technique of diesel oil, such method for preparing catalyst is inappropriate.And the another kind of method of preparing bifunctional catalyst is the catalyst with nucleocapsid structure that adopts the method for rolling moulding to prepare.In the process of rolling moulding, different time adds the powder that contains different activities component, can in catalyst granules, form the structure with radially layered, different activities component is distributed in different radial depths, this has also just formed the zones of different in same catalyst granules with multiple catalysis, and between the active component of difference in functionality, only have the attaching space of a sphere, therefore between different active components influence each other very little.Such preparation method is favourable for Methanol for diesel oil.
Summary of the invention
The object of the present invention is to provide a kind of can be the egg-shell catalyst with nucleocapsid structure that is rich in the high-quality diesel oil of straight-chain hydrocarbons by methanol conversion.This catalyst is to adopt the method for rolling moulding to prepare, and has also introduced the auxiliary agent with heat conduction function in forming process, and the kernel of this catalyst is the component with Fischer-Tropsch complex functionality, and outer shell is the component with Methanol Decomposition function.
Methyl alcohol being changed into the process of diesel oil, is the consecutive process being cascaded by two reactions in fact, is first that methyl alcohol is decomposed into synthesis gas on catalyst, is and then that synthesis gas changes diesel oil into through Fischer-Tropsch synthesis.The catalyst of the eggshell type of a kind of rotational forming provided by the invention has the ability of decomposing the ability that methyl alcohol is synthesis gas and synthesis gas being converted into diesel oil, so this catalyst provided by the invention is to have bifunctional catalyst simultaneously.
Methanol Decomposition is that the reaction of synthesis gas is the reaction of a heat absorption, and synthesis gas is the process of a heat release through the synthetic process that changes diesel component into of Fischer-Tropsch, the present invention is exactly the method by roller forming, the component of two kinds of catalysis is incorporated into same catalyst particles intragranular, and make them in the each autocatalysis of performance, the reaction heat that allows the methanol decomposition reaction of carrying out in kernel utilize Fischer-Tropsch in shell to discharge in synthetic, realize the coupling of heat absorption and release process, thereby when reducing whole process energy consumption, also improve the selective of equilibrium conversion and target product.Therefore, the catalyst of this eggshell type provided by the invention, not only has double-function catalyzing performance, also has the heat exchange function of coupling Process of absorption or liberation of heat process.In order to promote the heat exchange efficiency of catalyst granules inside, improve heat exchange rate, in the present invention, in catalyst granules forming process, add the auxiliary agent with heat conduction function, graphite is because its good heat conductivility, and possesses resistance to elevated temperatures, so use as heat conduction auxiliary agent in the present invention, add in nodulizer after mixing with the powder of other component.
Egg-shell catalyst particle provided by the invention is in the process of rolling moulding, the powder with the active component of different catalysis successively adds according to time sequencing, first be to add in nodulizer after the powder of component with Fischer-Tropsch complex functionality is mixed with heat conduction auxiliary agent, the thickness forming when this component reaches after required numerical value, powder after mixing with heat conduction auxiliary agent by the component with Methanol Decomposition function again continues rolling moulding, reach after required diameter to particle, moulding completes.
The egg-shell catalyst that the invention provides a kind of moulding of rolling can be converted into methyl alcohol the product that is rich in diesel component.Except having the characteristic of double-function catalyzing, be coupled the in addition good heat exchange function of Process of absorption or liberation of heat of the present invention, therefore has better diesel oil selective.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed.
The following examples are only for the present invention that explains in detail, and limit the scope of the invention never in any form.
Embodiment 1
Aluminium colloidal sol taking density as 0.7g/ml and concentration are mixed with adhesive (wherein aluminium colloidal sol and aqueous solution of nitric acid volume ratio are 15:1) as 5% aqueous solution of nitric acid, by uniform ground and mixed cobalt oxide, aluminium oxide and graphite (Co:Al=1:9 mol ratio, the mass ratio of graphite and Co and Al oxide is 1:100) powder pour in A nodulizer, the adhesive spraying into atomization contacts, rolling moulding, in the time that the spherolite radius of moulding reaches 2.5mm, spherolite enters in B nodulizer after rolling out from A nodulizer, in B nodulizer, there is the uniform cupric oxide of ground and mixed, zinc oxide and aluminium oxide, and the powder of graphite (Cu:Zn:Al=1:1:6 mol ratio, graphite and Cu, the mass ratio of Zn and Al oxide is 1:5), under the adhesive effect spraying in atomization, continue to roll and be formed into the spherical of diameter 10mm, leave B nodulizer.Now there is the Active components distribution of Fischer-Tropsch complex functionality in the kernel area of radius≤2.5mm, and the Active components distribution with Methanol Decomposition function at radius in the shell region between 2.5mm to 5mm, heat conduction auxiliary agent graphite is to be distributed in whole particle.The roasting at 400 DEG C of spheric granules after moulding, after 2 hours, is obtained to spheric catalyst particle.Such catalyst granules is packed in the fixed bed reactors that internal diameter is 80mm, height of formation is the beds of 320mm, flow with 1000ml/min passes into methyl alcohol, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 29%, all in product, CO2 accounts for 25%, and in hydrocarbon product, methane selectively is 12%, and C10 above (represent diesel oil with the above component of C10 here, lower together) selectively reach 49%.
Comparative example 1
Aluminium colloidal sol taking density as 0.7g/ml and concentration are mixed with adhesive (wherein aluminium colloidal sol and aqueous solution of nitric acid volume ratio are 15:1) as 5% aqueous solution of nitric acid, the powder of uniform ground and mixed cobalt oxide and aluminium oxide (Co:Al=1:9 mol ratio) is poured in A nodulizer, the adhesive spraying into atomization contacts, rolling moulding, in the time that the spherolite radius of moulding reaches 2.5mm, spherolite enters in B nodulizer after rolling out from A nodulizer, in B nodulizer, there is the uniform cupric oxide of ground and mixed, the powder (Cu:Zn:Al=1:1:6 mol ratio) of zinc oxide and aluminium oxide, under the adhesive effect spraying in atomization, continue to roll and be formed into the spherical of diameter 10mm, leave B nodulizer.Now there is the Active components distribution of Fischer-Tropsch complex functionality in the kernel area of radius≤2.5mm, and the Active components distribution with Methanol Decomposition function at radius in the shell region between 2.5mm to 5mm.The roasting at 400 DEG C of spheric granules after moulding, after 2 hours, is obtained to spheric catalyst particle.Such catalyst granules is packed in the fixed bed reactors that internal diameter is 80mm, height of formation is the beds of 320mm, flow with 1000ml/min passes into methyl alcohol, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 28%, all in product, CO2 accounts for 21%, in hydrocarbon product, methane selectively is 14%, and more than C10 selectively reaches 45%.
Claims (4)
1. the egg-shell catalyst of the moulding of rolling, it is characterized in that, this catalyst has the function of the methanol decomposition process of coupling heat absorption and the Fischer-Tropsch building-up process of heat release, methyl alcohol can be converted into diesel oil distillate, its outer shell is the active component with Methanol Decomposition function, in kernel, for to there is the active component of Fischer-Tropsch complex functionality, and in rolling forming process, add heat conduction auxiliary agent.
2. the egg-shell catalyst of a kind of moulding of rolling according to claim 1, is characterized in that, the catalyst activity component in outer shell with Methanol Decomposition function contains one or several elements in Cu, Zn, Al and Si.
3. the egg-shell catalyst of a kind of moulding of rolling according to claim 1, is characterized in that, the active component in kernel with Fischer-Tropsch complex functionality catalyst contains one or several elements in Co, Fe, Al and Si.
4. the egg-shell catalyst of a kind of moulding of rolling according to claim 1, is characterized in that, the heat conduction auxiliary agent adding in forming process is graphite, and the mass ratio of graphite and other powder is between 1/100 to 1/5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410451833.XA CN104162431A (en) | 2014-09-09 | 2014-09-09 | Roll forming type egg shell type catalyst |
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| CN201410451833.XA CN104162431A (en) | 2014-09-09 | 2014-09-09 | Roll forming type egg shell type catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268554A (en) * | 2016-08-16 | 2017-01-04 | 中国石油大学(北京) | A kind of core-shell type MOFs composite particles and its preparation method and application |
| CN112138714A (en) * | 2020-09-24 | 2020-12-29 | 大连理工大学 | Rolling sweet-ball-type molded sulfur-resistant low-temperature denitration catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616735A (en) * | 2007-01-30 | 2009-12-30 | Gtl.F1公司 | The preparation method of fischer-tropsch catalysts |
| CN103157492A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Shell distribution catalyst and preparation method thereof |
| CN103492074A (en) * | 2011-04-26 | 2014-01-01 | 韩国化学研究院 | Catalyst for fischer-tropsch synthesis having excellent heat transfer capability |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
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2014
- 2014-09-09 CN CN201410451833.XA patent/CN104162431A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616735A (en) * | 2007-01-30 | 2009-12-30 | Gtl.F1公司 | The preparation method of fischer-tropsch catalysts |
| CN103492074A (en) * | 2011-04-26 | 2014-01-01 | 韩国化学研究院 | Catalyst for fischer-tropsch synthesis having excellent heat transfer capability |
| CN103157492A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Shell distribution catalyst and preparation method thereof |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268554A (en) * | 2016-08-16 | 2017-01-04 | 中国石油大学(北京) | A kind of core-shell type MOFs composite particles and its preparation method and application |
| CN112138714A (en) * | 2020-09-24 | 2020-12-29 | 大连理工大学 | Rolling sweet-ball-type molded sulfur-resistant low-temperature denitration catalyst and preparation method and application thereof |
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Application publication date: 20141126 |